Three-dimensional conductive electrode for solar cell

ABSTRACT

A photovoltaic device and method include forming a plurality of pillar structures in a substrate, forming a first electrode layer on the pillar structures and forming a continuous photovoltaic stack including an N-type layer, a P-type layer and an intrinsic layer on the first electrode. A second electrode layer is deposited over the photovoltaic stack such that gaps or fissures occur in the second electrode layer between the pillar structures. The second electrode layer is wet etched to open up the gaps or fissures and reduce the second electrode layer to form a three-dimensional electrode of substantially uniform thickness over the photovoltaic stack.

BACKGROUND Technical Field

The present invention relates to photovoltaic devices, and moreparticularly to a device and method for fabricating a photovoltaicdevice structure with a textured electrode.

Description of the Related Art

With growing concern about low cost clean energy, solar power has againbecome a focal point for alternatives to fossil fuel energy production.Solar energy, while clean and sustainable, typically relies on expensivetechnologies for its implementation. These technologies include theincorporation of integrated circuits or integrated circuit technologyinto the fabrication of solar cells. The expense associated with currentsolar panels is a strong disincentive from moving in the direction ofsolar power.

Solar panels employ photovoltaic cells to generate current flow. When aphoton hits silicon, the photon may be transmitted through the silicon,reflected off the surface, or absorbed by the silicon if the photonenergy is higher than the silicon band gap value. This generates anelectron-hole pair and sometimes heat, depending on the band structure.The greater the absorption the greater the efficiency of the cell.

Textured structures have been employed to increase the absorptionefficiency. However, challenges arise at several points in the process.One such problem includes the formation of a bottom electrode. A bottomelectrode deposition occurs by forming a thick layer of electrodematerial and deep reactive ion etching (DRIE) the material to attempt toconform the bottom electrode material to the shape of the underlyingstructure. DRIE is a highly anisotropic etch process making theformation of the bottom electrode highly sensitive to thicknessvariations. A bottom electrode that is too thin results in seriesresistance problems and affects the efficiency of the solar cell.

SUMMARY

A photovoltaic device and method include forming a plurality of pillarstructures in a substrate, forming a first electrode layer on the pillarstructures and forming a continuous three-dimensional (3D) photovoltaicstack including an N-type layer, a P-type layer and an intrinsic layeron the first electrode. A second electrode layer is deposited over thephotovoltaic stack such that gaps or fissures occur in the secondelectrode layer between the pillar structures. The second electrodelayer is wet etched to open up the gaps or fissures and reduce thesecond electrode layer to form a three-dimensional electrode ofsubstantially uniform thickness over the 3D photovoltaic stack.

A method for forming a photovoltaic device includes forming a pluralityof pillar structures in a substrate; forming a first electrode layer onthe pillar structures; forming a continuous photovoltaic stack includingan N-type layer, a P-type layer and an intrinsic layer on the firstelectrode; depositing a second electrode layer over the photovoltaicstack such that gaps or fissures occur in the second electrode layerbetween the pillar structures; further depositing the second electrodelayer to enclose the fissures in the second electrode layer; and wetetching the second electrode layer reduce the second electrode layer andform a three-dimensional electrode over the photovoltaic stack.

A photovoltaic device includes a substrate layer having a plurality ofpillar structures formed therein, and a first electrode formed over thesubstrate layer and extending over the pillar structures. A continuousphotovoltaic stack is conformally formed over the first electrode, and asecond electrode is formed on the photovoltaic stack and includes gapsbetween the pillar structures buried within the second electrode.

These and other features and advantages will become apparent from thefollowing detailed description of illustrative embodiments thereof,which is to be read in connection with the accompanying drawings.

BRIEF DESCRIPTION OF DRAWINGS

The disclosure will provide details in the following description ofpreferred embodiments with reference to the following figures wherein:

FIG. 1 is a cross-sectional view of a photovoltaic device having aplurality of pillar structures with a first electrode and a photovoltaicstack formed thereon in accordance with one embodiment;

FIG. 2 is a cross-sectional view of the photovoltaic device of FIG. 1having a second electrode formed with gaps and fissures in accordancewith one embodiment;

FIG. 3A is a cross-sectional view of the photovoltaic device of FIG. 2having the second electrode wet etched in accordance with oneembodiment;

FIG. 3B is a scanning electron microscope image of the device after wetetching in FIG. 3A;

FIG. 4 is a cross-sectional view of the photovoltaic device of FIG. 1having a second electrode formed with gaps and fissures enclosed by thesecond electrode layer in accordance with another embodiment;

FIG. 5A is a cross-sectional view of the photovoltaic device of FIG. 4having the second electrode wet etched in accordance with oneembodiment;

FIG. 5B is a scanning electron microscope image of the device after wetetching in FIG. 5A; and

FIG. 6 is a flow diagram showing methods for fabricating a photovoltaicdevice in accordance with the present principles.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

In accordance with the present principles, devices and methods forfabricating photovoltaic devices are provided. The devices employ asubstrate layer having prefabricated structures configured to provide avertical component of a radiation absorption layer. The verticalcomponent may include a hill and trough structure having sides thatcarry the light absorbing material. The sides provide a depth toincrease the likelihood of absorption of the radiation. In this way, thestructures provide an inexpensive method that does not require expensivelithographic patterning and results in higher absorption efficiency.

In one embodiment, after forming the active radiation absorbing layers,a bottom electrode is formed by depositing a thick layer of bottomelectrode material followed by a wet etch. The wet etch takes advantageof the geometric gaps and crevices in the thick layer due to theunderlying textured structures to provide a more uniform and contouredbottom electrode. In another embodiment, the bottom electrode materialis formed so thick that the crevices and gaps are buried.

It is to be understood that the present invention will be described interms of given illustrative architectures for a solar cell; however,other architectures, structures, substrate materials and processfeatures and steps may be varied within the scope of the presentinvention. A circuit formed using these structures as described hereinmay be part of a design for an integrated circuit chip. The chip designmay be created in a graphical computer programming language, and storedin a computer storage medium (such as a disk, tape, physical hard drive,or virtual hard drive such as in a storage access network). If thedesigner does not fabricate chips or the photolithographic masks used tofabricate chips, the designer may transmit the resulting design byphysical means (e.g., by providing a copy of the storage medium storingthe design) or electronically (e.g., through the Internet) to suchentities, directly or indirectly. The stored design is then convertedinto the appropriate format (e.g., GDSII) for the fabrication ofphotolithographic masks, which typically include multiple copies of thechip design in question that are to be formed on a wafer. Thephotolithographic masks are utilized to define areas of the wafer(and/or the layers thereon) to be etched or otherwise processed.

Methods as described herein may be used in the fabrication of integratedcircuit chips and/or solar cells. The resulting integrated circuit chipsor cells can be distributed by the fabricator in raw wafer form (thatis, as a single wafer that has multiple unpackaged chips), as a baredie, or in a packaged form. In the latter case, the chip is mounted in asingle chip package (such as a plastic carrier, with leads that areaffixed to a motherboard or other higher level carrier) or in amultichip package (such as a ceramic carrier that has either or bothsurface interconnections or buried interconnections). In any case thechip is then integrated with other chips, discrete circuit elements,and/or other signal processing devices as part of either (a) anintermediate product, such as a motherboard, or (b) an end product. Theend product can be any product that includes photovoltaic devices,integrated circuit chips with solar cells, ranging from toys,calculators, solar collectors and other low-end applications to advancedproducts.

It will also be understood that when an element as a layer, region orsubstrate is referred to as being “on” or “over” another element, it canbe directly on the other element or intervening elements may also bepresent. In contrast, when an element is referred to as being “directlyon” or “directly over” another element, there are no interveningelements present. It will also be understood that when an element isreferred to as being “connected” or “coupled” to another element, it canbe directly connected or coupled to the other element or interveningelements may be present. In contrast, when an element is referred to asbeing “directly connected” or “directly coupled” to another element,there are no intervening elements present.

Referring now to the drawings in which like numerals represent the sameor similar elements and initially to FIG. 1, an illustrativephotovoltaic structure 100 is illustratively depicted in accordance withone embodiment. The photovoltaic structure 100 may be employed in solarcells, light sensors or other photovoltaic applications. Structure 100includes a substrate 102. The substrate 102 includes cone shaped pillars104. The pillars 104 may be fabricated by any number of processes, suchas forming mechanical grooves, employing a nanodot or other pattern andetching the substrate, etc. The substrate 102 may include a siliconmaterial, a glass or other etchable transparent substrate material. Asilicon substrate may include a single (monocrystalline) silicon or apolycrystalline silicon (polysilicon). While other substrate materialsmay be employed silicon based materials including glass are preferred.

The pillars 104 assist in increasing the surface area of absorption andprovide for radiation trapping between the pillars 104. The pillarstructures may be constructed to receive light with the pillars 104facing out (e.g., toward the light) or facing in. The pillars 104increase the surface area and therefore the collection efficiency in anyincident light direction as compared to a flat surface cell. The presentembodiments will be described in terms of the pillars 104 facing awayfrom the incident light in a final device structure. The pillars 104 mayinclude a height or about one micron, although larger or smaller pillarsare contemplated.

A first electrode layer 106 is formed on pillars 104 by a depositionprocess. The first electrode layer 132 may include a transparentconductive material such as a transparent conductive oxide (e.g., zincoxide, indium tin oxide, indium zinc oxide, etc.), ultra-thin metal(e.g., 20 nm or less in thickness) or other conductive structure. Thedeposition process may include a chemical vapor deposition (CVD) processor other suitable deposition process. A p-i-n diode stack 108 is formedover the first electrode 106. The stack 108 preferably includes a firstdoped layer (p-doped layer), and intrinsic layer (i-layer) and a seconddoped layer (n-doped layer). The stack 108 may be formed using a plasmaenhanced chemical vapor deposition (PECVD) process. The stack 108provides active areas for absorbing radiation and converting theradiation into charge flow as is known in the art. A plurality ofdifferent materials may be selected for the layers in stack 108. In oneparticularly useful embodiment, the first and second doped layers mayinclude doped polycrystalline/microcrystalline silicon and the intrinsiclayer may include undoped amorphous silicon. It should be understoodthat other layers and features may be included, such as contact layers,etc., or even multiple photovoltaic stacks may be employed.

Referring to FIG. 2, a second electrode 110 is formed on the stack 108.The second electrode 110 may include a transparent conductive materialsuch as a transparent conductive oxide (e.g., zinc oxide, doped zincoxide, tin oxide, a fluorine-doped tin oxide, indium tin oxide, indiumzinc oxide, etc.), metal or other conductive structure. The depositionprocess may include a sputtering process, other physical vapordeposition process or other suitable deposition process. In thisembodiment, second electrode 110 forms a bottom electrode for the device100.

In one embodiment, the bottom electrode 110 includes ZnO and is formedas deposited to a height, h₁ of about 2 microns with the pillars 104being about 1 micron in width. The final etched thickness of theelectrode 110 on the pillars 104 is between about 100 nm and 500 nm. Inthis embodiment, gaps/fissures/grain boundaries 112 form between pillars104, and will be employed to form a final configuration of the bottomelectrode 110 (FIG. 3A).

Referring to FIG. 3A, a wet etch process is employed to reduce the sizeof the, as deposited, bottom electrode 110 and to exploit thegaps/fissures 112. The wet etching process results in a simultaneousreduction and narrowing of the shape of the bottom electrode 110 toprovide a more conforming profile. The wet etching process may include ahydrochloric acid (HCl) although other etchants may be employed, e.g.,HF, HNO₃, etc. In addition, the wet etching process provides betterprocess control for the bottom electrode 110 thickness and is much moreinexpensive than deep reactive ion etching. The bottom electrode 110 inthis embodiment, forms a three-dimensional electrode and includes atextured surface conforming with the between pillars 104.

Additional layers may be formed before or on the bottom electrode 110.These layers may include reflective materials. A back reflector layermay be formed with a reflective surface to reflect transmitted lightback toward the light absorption layer. The surface preferably mayinclude a highly reflective material, such as silver (Ag), chromium(Cr), etc.

Referring to FIG. 3B, a scanning electron microscope (SEM) image showsthe results of the wet etch of FIG. 3A. The image of FIG. 3B is theresult of a 1:200 HCl:H₂O wet etch for 20 seconds. Other wet etchsolutions and etch times may also be employed.

Referring to FIG. 4, a photovoltaic device 200 in accordance withanother embodiment is illustratively shown. Beginning with the structuredepicted in FIG. 1, a bottom electrode layer 116 is deposited over thestack 108 on pillars 104. The deposition may be performed by sputteringor other deposition process. The bottom electrode layer 116 includes asufficient thickness to enclose gaps/fissures 118. The bottom electrodelayer 116 may include a transparent conductive oxide (TCO), such as, atin oxide, a fluorine-doped tin oxide (SnO₂:F, or “FTO”), a zinc oxide,a doped zinc oxide (e.g., ZnO:Al), indium tin oxide (ITO) or othersuitable materials. The bottom electrode layer 116 may include an asdeposited height h₂ of between about 3 microns to about 5 microns. Thefinal thickness of the bottom electrode layer 116 in this embodiment isabout 3-4 microns.

Referring to FIG. 5A, the photovoltaic structure 200 may be subjected toa wet etch process as described above to reduce the bottom electrodelayer 116 to a desired thickness and to further provide a contoured ortextured surface 120 which may be employed to redirect incidentradiation toward light absorption layers in the stack 108. The bottomelectrode layer 116 in this embodiment forms a three-dimensionalelectrode and includes a textured surface 120 and buried gaps/fissures118 between pillars 104.

Referring to FIG. 5B, a scanning electron microscope (SEM) image showsthe results of the wet etch of FIG. 5A. The image of FIG. 5B is theresult of an HF etch for 20 minutes. Other wet etch solutions and etchtimes may also be employed.

Referring to FIG. 6, methods for forming a photovoltaic device inaccordance with illustrative embodiments are illustratively shown. Theflowchart/block diagram in the FIG. 6 illustrates the architecture,functionality, and operation of possible implementations of methodsaccording to various embodiments of the present invention. It should benoted that, in some alternative implementations, the functions noted inthe blocks may occur out of the order noted in the figures. For example,two blocks shown in succession may, in fact, be executed substantiallyconcurrently, or the blocks may sometimes be executed in the reverseorder, depending upon the functionality involved.

In block 202, a substrate layer is provided. In attempting to reducecost, the present principles prefer the use of a non-semiconductorsubstrate layer material. For example, the substrate may include glass.In block 204, a plurality of pillar structures are formed in thesubstrate. This may include mechanically forming a plurality of grooves,chemically etching the pillar structures, etc. The pillar structurespreferably include a depth of less than about two microns, morepreferably one micron. Larger dimensions may be employed; however, theactive layers are preferably nanoscale and a depth of about a micron ispreferable. Other methods include using 3D structuring such asembossing, stamping, molding, etc. for forming pillars.

In block 206, a first electrode layer is formed on the pillarstructures. The first electrode layer may include a transparentconductive oxide, an ultrathin metal or other transparent conductivematerial. The first electrode may be a few nanometers thick, e.g., 5nm-20 nm for ultrathin metal or conductive materials that arenon-transparent and 200 nm-300 nm for transparent conductive oxide. Inblock 208, a continuous photovoltaic stack is formed on the firstelectrode. The stack may include an N-type layer, a P-type layer and anintrinsic layer disposed between the N and P-type layers. Additionalphotovoltaic stacks and other layers may also be formed on thecontinuous photovoltaic stack in block 210.

In one embodiment, in block 212, a second electrode layer is formed overthe photovoltaic stack(s) and includes a thickness such that gaps orfissures occur in the second electrode layer between the pillarstructures. The thickness of the second electrode layer may be greaterthan one micron, and more preferably about 2 microns, although thickerlayers may be employed. The second electrode layer preferably includes atransparent conductive oxide, such as e.g., ZnO, and the transparentconductive oxide may be applied by sputtering.

In block 214, the second electrode layer is wet etched to open up thegaps or fissures and reduce the second electrode layer to form athree-dimensional electrode of substantially uniform thickness over thephotovoltaic stack. The wet etching may include employing hydrochloricacid or the like.

In another embodiment, in block 216, the second electrode layer isfurther deposited to enclose the fissures in the second electrode layer.The depositing includes a thickness of between about 3 microns to about5 microns. In block 218, the second electrode layer is wet etched toreduce the second electrode layer and form a three-dimensional electrodeover the photovoltaic stack. The wet etching may include employinghydrochloric acid or the like. In block 220, additional processing maybe performed including forming additional layers or features.

Having described preferred embodiments for a three-dimensionalconductive electrode for a solar cell (which are intended to beillustrative and not limiting), it is noted that modifications andvariations can be made by persons skilled in the art in light of theabove teachings. It is therefore to be understood that changes may bemade in the particular embodiments disclosed which are within the scopeof the invention as outlined by the appended claims. Having thusdescribed aspects of the invention, with the details and particularityrequired by the patent laws, what is claimed and desired protected byLetters Patent is set forth in the appended claims.

What is claimed is:
 1. A method for forming a photovoltaic device,comprising: forming a plurality of pillar structures in a substrate;forming a first electrode layer on the pillar structures; forming aphotovoltaic stack on the first electrode layer; depositing a secondelectrode layer over the photovoltaic stack such that air gaps occur inthe second electrode layer between the pillar structures; furtherdepositing the second electrode layer to enclose the air gaps in thesecond electrode layer, wherein a single air gap is enclosed within thesecond electrode layer so that a single air gap between each set ofadjacent pillar structures extends in a stack direction for a majorityof the height of the pillar structures; and wet etching the secondelectrode layer to reduce the second electrode layer and to form athree-dimensional electrode over the photovoltaic stack.
 2. The methodas recited in claim 1, wherein the second electrode layer includes atransparent conductive oxide and the step of depositing includesdepositing the second electrode layer by sputtering.
 3. The method asrecited in claim 2, wherein the transparent conductive oxide includesZnO.
 4. The method as recited in claim 1, wherein the substrate includesglass.
 5. The method as recited in claim 1, wherein wet etching includesemploying hydrochloric acid.
 6. The method as recited in claim 1,wherein depositing includes depositing the second electrode layer to athickness of between about 3 microns to about 5 microns.
 7. Aphotovoltaic device, comprising: a first electrode extending over pillarstructures; a photovoltaic stack conformally formed over the firstelectrode; and a second electrode formed on the photovoltaic stack andincluding air gaps between the pillar structures buried within thesecond electrode, wherein a single air gap is enclosed within the secondelectrode layer so that a single air gap extends in a stack directionfor a majority of the height of the pillar structures.
 8. The device asrecited in claim 7, wherein the photovoltaic stack includes a P-typelayer and an N-type layer.
 9. The device as recited in claim 8, whereinan intrinsic layer present between the P-type layer and the N-typelayer.
 10. The device as recited in claim 7, wherein the substrateincludes glass.
 11. The device as recited in claim 7, further comprisingat least one additional continuous photovoltaic stack formed on thecontinuous photovoltaic stack.
 12. The device as recited in claim 7,wherein the second electrode includes a thickness of between about 3 and5 microns.
 13. The device as recited in claim 7, wherein the secondelectrode includes a three-dimensional texture surface that is oppositea surface of the second electrode in contact with the pillar structures.14. The device as recited in claim 7, wherein the second electrode layerincludes a transparent conductive oxide.
 15. The device as recited inclaim 14, wherein the transparent conductive oxide includes ZnO.
 16. Amethod for forming a photovoltaic device, comprising: forming aphotovoltaic stack on the first electrode layer that is present onpillar structures; depositing a second electrode layer over thephotovoltaic stack such that air gaps occur in the second electrodelayer between the pillar structures; further depositing the secondelectrode layer to enclose the air gaps in the second electrode layer,wherein a single air gap is enclosed within the second electrode layerso that a single air gap between each set of adjacent pillar structuresextends in a stack direction for a majority of the height of the pillarstructures; and wet etching the second electrode layer to reduce thesecond electrode layer and to form a three-dimensional electrode overthe photovoltaic stack.
 17. The method as recited in claim 16, whereinthe second electrode layer includes a transparent conductive oxide andthe step of depositing includes depositing the second electrode layer bysputtering.
 18. The method as recited in claim 17, wherein thetransparent conductive oxide includes ZnO.
 19. The method as recited inclaim 16, wherein the substrate includes glass.
 20. The method asrecited in claim 16, wherein wet etching includes employing hydrochloricacid.